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21.
Typical cis-PtA(2)G(2) models of key DNA lesions formed by cis-type Pt anticancer drugs are very dynamic and difficult to characterize (A(2) = diamine or two amines; G = guanine derivative). Retro models have A(2) carrier ligands designed to decrease dynamic motion without eliminating any of three possible conformers with bases oriented head-to-tail (two: DeltaHT and LambdaHT) or head-to-head (one: HH). All three were found in NMR studies of eight Me(2)DABPtG(2) retro models (Me(2)DAB = N,N'-dimethyl-2,3-diaminobutane with S,R,R,S and R,S,S,R configurations at the chelate ring N, C, C, and N atoms, respectively; G = 5'-GMP, 3'-GMP, 5'-IMP, and 3'-IMP). The bases cant to the left (L) in (S,R,R,S)-Me(2)DABPtG(2) adducts and to the right (R) in (R,S,S,R)-Me(2)DABPtG(2) adducts. Relative to the case in which the bases are both not canted, canting will move the six-membered rings closer in to each other ("6-in" form) or farther out from each other ("6-out" form). Interligand interactions between ligand components near to Pt (first-first sphere communication = FFC) or far from Pt (second-sphere communication = SSC) influence stability. In typical cases at pH < 8, the "6-in" form is favored, although the larger six-membered rings of the bases are close. In minor "6-out" HT forms, the proximity of the smaller five-membered rings could be sterically favorable. Also, G O6 is closer to the sterically less demanding NH part of the Me(2)DAB ligand, possibly allowing G O6-NH hydrogen bonding. These favorable FFC effects do not fully compensate for possibly stronger FFC dipole effects in the "6-in" form. SSC, phosphate-N1H cis G interactions favor LambdaHT forms in 5'-GMP and 5'-IMP complexes and DeltaHT forms in 3'-GMP and 3'-IMP complexes. When SSC and FFC favor the same HT conformer, it is present at >90% abundance. In six adducts [four (S,R,R,S)-Me(2)DABPtG(2) and (R,S,S,R)-Me(2)DABPtG(2) (G = 3'-GMP and 3'-IMP)], the minor "6-out" HT form at pH approximately 7 becomes the major form at pH approximately 10, where G N1H is deprotonated, because the large distance between the negatively charged N1 atoms minimizes electrostatic repulsion and probably because the G O6-(NH)Me(2)DAB H-bond (FFC) is strengthened by N1H deprotonation. At pH approximately 10, phosphate-negative N1 repulsion is an unfavorable SSC term. This factor disfavors the LambdaHT R form of two (R,S,S,R)-Me(2)DABPtG(2) (G = 5'-GMP and 5'-IMP) adducts to such an extent that the "6-in" DeltaHT R form remains the dominant form even at pH approximately 10. 相似文献
22.
The electric quadrupole interaction at the Hf site in the cubic HfV2 compound, which shows lattice instability when cooled below 120 K, has been studied using the 482 keV (5/2+) state in181Ta. The time differential perturbed angular correlation (TDPAC) studies involving (133+136)-482 keV - cascade at room temperature show that only a fraction of181Ta nuclei see a cubic symmetry while the remaining experience a weak, randomly oriented, electric quadrupole interaction described by a Gaussian frequency distribution with Q=6.1±1.0 Mrad/sec and the relative width =0.5. There is a dramatic change in TDPAC pattern indicating a phase transition when the compound is cooled down to 77 K. At this temperature the quadrupole interaction frequency is found to be Q=40.6±3.0 Mrad/sec with =0.35. The experimentally observed EFG both at the Hf and the V sites are compared to the theoretical estimates based on point charge model. 相似文献
23.
Summary The iodine number of twenty-two samples of different fats and oils is determined by 131I, according to the radiometric method. The values obtained for such samples lie between 7.2 and 154.9. The method is applicable with reproducible results and is recommended to cover any stage of unsaturation.
Zusammenfassung Die Jodzahl von 22 Proben verschiedener Öle und Fette wird radiometrisch unter Benutzung von Jod-131 bestimmt. Die erhaltenen Werte liegen zwischen 7,2 und 154,9. Das Verfahren liefert reproduzierbare Ergebnisse und ist für jeden Grad von Ungesättigtheit anwendbar.相似文献
24.
Sullivan ST Saad JS Fanizzi FP Marzilli LG 《Journal of the American Chemical Society》2002,124(8):1558-1559
The cisplatin anticancer drug preferentially attacks the GG sequence of DNA duplexes. Virtually all DNAs containing the key G*G* lesion (G* = N7 platinated G) have large distortions in the cross-link (G*G*) base pair (bp) step and also in the adjacent Lippard (XG*) bp step, making the adducts very different from B-form DNA in the XG*G* region. The XG*G* strand in duplexes also differs in several ways from single-strand (ss) models with G*G* and XG*G* sequences. In the duplex, the X residue has an N sugar, the 5'-G* and 3'-G* bases have slight "R" canting (3'-G* H8 atom toward the 5'-G* base), and there is no or weak H-bonding by the NH3 ligands. In most XG*G* ss models, X has an S sugar, the 5'-G* base normally cants strongly toward the 3'-G* base (L canting), and the NH3 forms an H-bond. Well-defined ss models exist in the solid state, but dynamic motion obscures the properties of the ss models in solution. In this work, we employ retro models (better defined, less dynamic ss models) to understand the differences between duplex and ss models. The retro models in this study lack carrier ligand NH's, thus eliminating H-bonding. To correlate previous ss solid-state models with our solution work, we constructed hybrid molecules by overlaying parts of known structures. The combined model and experimental information indicates that the X N-pucker is not favorable in L-canted ss models, that X residue steric effects (not H-bonding) favor L canting in ss models, that X N-pucker is needed for favorable WC hydrogen bonding and stacking interactions in duplexes, and that X N-pucker minimizes X base clashes with bases in the complementary strand in duplexes. The R canting minimizing clashes between the X and G* residues of the Lippard bp step (independent of X pucker) and the repositioning of the X residue base caused by the change from S-pucker to N-pucker together lead to the unusual features of the Lippard bp step in the duplex. 相似文献
25.
An unprecedented one-pot reductive trimerization of aromatic aldehydes to 1,2,3-triaryl-2-propen-1-ones as well as tandem reductive coupling-rearrangements of aryl ketones to pinacolone analogues was efficiently achieved using tetrachlorosilane-zinc at room temperature. 相似文献
26.
M. B. Alamin A. A. Mhapes A. M. Bejey A. Sadek R. H. Atweer K. Dubali Daw M. Saad 《Journal of Radioanalytical and Nuclear Chemistry》2007,271(1):247-250
Since there is no database in Libya defining the intake of the individuals from different essential (minor and trace) and
toxic elements provided through food, drinking water and aerosol, a project has been proposed with the cooperation of IAEA
to determine the concentration of a number of elements such as Cs, Fe, Cr, Rb, Sc, Se, Co, Zn in the three mentioned sources.
Emphasis was placed on the use of nuclear and nuclear-related techniques. In this paper, the primary results are presented
for the concentration of minor and trace elements in some vegetables, spices and other foods which are widely used in the
Libyan meals. Instrumental neutron activation analysis utilizing a 10 MW water pool reactor and a γ-ray spectroscopy facility
was employed. For quality control, certified reference materials were analyzed simultaneosly with the samples which show good
agreements compared with the certified data. Emphasis was given to both elements iron and zinc for their importance. 相似文献
27.
Saad Zagloul Rida 《Applicable analysis》2013,92(1-2):93-102
We derive none some explicit formula for the power of fractional order (differential and integral) operators. 相似文献
28.
29.
Tadros Soad M. Soliman Yasser S. Beshir W. B. Saad Gamal R. Ali LailaI. 《Journal of Radioanalytical and Nuclear Chemistry》2021,329(1):463-473
Journal of Radioanalytical and Nuclear Chemistry - Radiation-induced Ag° nanoparticles (NPs) in silver nitrate gel dosimeter incorporating various components was investigated in the dose range... 相似文献
30.